การใช ยางธรรมชาต (NR) ผสมก บยางไนไตรล (NBR)

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1 การใช ยางธรรมชาต (NR) ผสมก บยางไนไตรล (NBR) ( ) CH 2 CH CH CH 2 ) ( CH 2 CH 3 H C C CH 2 CH 2 CH n C N Dr. Nittaya Rattanasom 2 June 2005

2 ยางธรรมชาต (Natural Rubber; NR) Hevea brasiliensis CH 3 H C C CH 2 CH 2 n cis-1,4-polyisoprene สมบ ต เช งกลส ง ราคาถ กกว า NBR แต ไม ทนน าม น

3 ยางไนไตรล (Acrylonitrile Butadiene Rubbers, Nitrile Rubber; NBR) Copolymer ของ ( ) CH 2 CH CH CH 2 ) ( CH 2 CH ปร มาณ AN ~ 18-48% C N ทนน าม นได ด แต สมบ ต เช งกลต าหากไม ผสม filler

4 Nitrile Rubber; NBR (ต อ) %AN 1. T g low temp. performance 2. resilience 3. elasticity process smoother 4. fuel & oil resistance 5. strength 6. heat resistance 7. gas permeability die swell

5 ป ญหาของ NR/NBR blends Differing in polarity - Poor compatibility - High interfacial tension - Limit mixing at the interface - Limit opportunity for crosslinking bet. NR/NBR - Poor phase morphology large phase sizes - Maldistribution of crosslinks M.V. Lewan, Blends of Natural Rubber, Chapman and Hall, London, 1998, 53.

6 Effect of accelelators on 50/50 NR/NBR41 blends Table: Masterbatch formulation Ingredients Stearic acid ZnO TMQ phr Semi-EV curing system sulphur : accelerator ~ 1:1 M.V. Lewan, Blends of Natural Rubber, Chapman and Hall, London, 1998, 53.

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10 Crosslink density distribution VS. Accelerators

11 Figure: Dependence of tensile strength on crosslink density ratio of 50:50 NR:NBR41 gum blends cured at 150 o C.

12 Phase morphology NBR NR Figure: Phase contrast micrograph of a 50:50 NR:NBR41 gum blend vulcanizate

13 Interfacial strength low tensile strength High tensile strength Figure: TEM micrograph of a 50:50 NR:NBR41 gum blend vulcanizate prepared for network visualization

14 180 o C 150 o C

15 50/50 NR/NBR34 BLENDS Figure: Crosslink density distributions in 50:50 NR:NBR34 of gum blends cured at 150 o C.

16 Improvement blends of highly incompatible elastomers NR/NBR Using compatibilizers - NR/PMMA graft copolymer (*MG30) - Chloroprene Adding carbon black *MG30 = a mixture of graft copolymer with ungrafted NR

17 Improving the Morphology and Properties of NR/NBR Blends with MG30 K.G. Karnika de Silva and M. V. Lewan Blends of Natural Rubber, Chapman and Hall, London, 1998, 68.

18 NBR NBR NR Phase contrast Micrograph NR 50:50 NR:NBR41 65:35 NR:NBR41 50:50 MG30:NBR41 10:40:50 NR:MG30:NBR41 Figure: STEM micrographs of various gum vulcanizates

19 50:50 NR:NBR 40:15:45 NR:MG30:NBR 25:25:50 NR:MG30:NBR 50:50 MG30:NBR Figure: STEM micrographs of NR/MG30/NBR28C45 gum vulcanizates

20 Table: Physical properties of NR:NBR41C80 blends cured with S/TMTD (1.5/0.6 phr) NR:MG30:NBR M100 (MPa) Tensile strength (MPa) 25:0: EB (%) *Oil swell ASTM#1 (%) :20.5: :0: :41: :0: :61.5: *Volume swelling after 70 h at 100 o C

21 Table: Physical properties of NR:NBR41C80 blends cured with S/TBBS (1.3/1.7 phr) NR:MG30:NBR M100 (MPa) Tensile strength (MPa) 65:15: EB (%) Oil swell ASTM#1 (%) :15: :15: :5: :10: :15: :20: :15: :15:

22 Table: NR:MG30:NBR blends with high tensile strength NR:MG30:NBR NBR grade M100 (MPa) 55:5:40 NBR41C Tensile strength (MPa) EB (%) :10:40 NBR41C :5:50 NBR41C :10:50 NBR41C :15:25 NBR28C :30:40 NBR28C *Cured with S/TBBS (1.3/1.17 phr)

23 Improving the Morphology and Properties of NR/NBR Blends with Polychloroprene H Cl C = C ( CH 2 CH 2 ) n Chloroprene Krisna Kongsin and M.V. Lewan, Blends of Natural Rubber, Chapman and Hall, London, 1998, 80.

24 Cure systems for NR/CR/NBR blends Table: Masterbatch formulations (phr) SMR L Krynac CR ZnO Stearic acid TMQ Table: Cure systems for NR/CR/NBR blends (phr) S CBS MBS TBBS TBTD TETD

25 50:50 NR:NBR34 Acc M300 (MPa) TS (MPa) EB (%) CBS CBS/TBTD CBS/TETD MBS MBS/TBTD MBS/TETD TBBS TBBS/TBTD TBBS/TETD

26 40:10:50 NR:CR:NBR34 Acc M300 (MPa) TS (MPa) EB (%) CBS CBS/TBTD CBS/TETD MBS MBS/TBTD MBS/TETD TBBS TBBS/TBTD TBBS/TETD

27 50:10:40 NR:CR:NBR34 Acc M300 (MPa) TS (MPa) EB (%) CBS CBS/TBTD CBS/TETD MBS MBS/TBTD MBS/TETD TBBS TBBS/TBTD TBBS/TETD

28 50:20:30 NR:CR:NBR34 Acc M300 (MPa) TS (MPa) EB (%) CBS CBS/TBTD CBS/TETD MBS MBS/TBTD MBS/TETD TBBS TBBS/TBTD TBBS/TETD

29 Effect of CR content on crosslink density distribution of gum blends 50:50 NR:NBR34 40:10:50 NR:CR:NBR34 50:10:40 NR:CR:NBR34 50:20:30 NR:CR:NBR34

30 Table: Physical properties of 50:5:45 NR:CR:NBR34 blends Acc M300 Tensile strength EB (%) system (MPa) (MPa) CBS CBS/TBTD CBS/TETD NBR Crosslink density distribution of 50:5:45 NR:CR:NBR34 STEM Micrograph of 50:5:45 NR:CR:NBR34

31 40:10:50 NR:CR:NBR34 50:10:40 NR:CR:NBR34 50:5:45 NR:CR:NBR34 50:20:30 NR:CR:NBR34 40:10:50 NR:CR:NBR41 50:5:45 NR:CR:NBR34 (+20 phr N phr CaCO 3 ) Figure: STEM micrographs of various gum blends

32 Relationship among Mooney viscosity, relative tensile strength and types of filler of 20:80 NR:NBR blends - C. Sirisinha, S. Baulek-Limcharoen and J. Thunyarittikron, J. Appl. Polym. Sci. 2003, 87, 83.

33 *Oil resistance measurement TS rel = TS after /TS before Immerse specimens in hydraulic oil (ASTM oil No.5) at RT for 70 h

34 Fillers Figure: Relationship among MV, rel.ts and types of filler of 20:80 NR:NBR blends

35 a) gum b) untreated silica c) silane-treated silica d) N220 CB f) N660 CB e) N330 CB Figure: Optical micrographs of 20:80 NR:NBR blends with various types of filler

36 Relationship among Mooney viscosity, relative tensile strength, morphology and rotor speed of 20:80 NR:NBR blends C. Sirisinha, S. Baulek-Limcharoen and J. Thunyarittikron, J. Appl. Polym. Sci. 2003, 89, 1156.

37 40 rpm 55 rpm 45 rpm 60 rpm x200 Figure: Relationship among MV, rel.ts, morphology and rotor speed of 20:80 NR:NBR blends

38 Relationship among Mooney viscosity, relative tensile strength, morphology and mixing time of 20:80 NR:NBR blends C. Sirisinha, S. Baulek-Limcharoen and J. Thunyarittikron, J. Appl. Polym. Sci. 2003, 89, 1156.

39 15 min 25 min 20 min 30 min 40 min x400 Figure: Relationship among MV, rel.ts, morphology and mixing time of 20:80 NR:NBR blends

40 References 1. M.V. Lewan, Blends of Natural Rubber, Chapman and Hall, London, 1998, K.G. Karnika de Silva and M. V. Lewan Blends of Natural Rubber, Chapman and Hall, London, 1998, Krisna Kongsin and M.V. Lewan, Blends of Natural Rubber, Chapman and Hall, London, 1998, C. Sirisinha, S. Baulek-Limcharoen and J. Thunyarittikron, J. Appl. Polym. Sci. 2003, 87, C. Sirisinha, S. Baulek-Limcharoen and J. Thunyarittikron, J. Appl. Polym. Sci. 2003, 89, 1156.

41 Swollen-state 1 H NMR

42 Figure: Dependence of tensile strength of NR/NBR41 gum blend vulcanizates on swelling restriction ratio.

43 High temperature vulcanization Figure: Crosslink density distributions in 50:50 NR:NBR41 of gum blends cured at 180 o C.

44 Table: Physical properties of NR:NBR41C80 blends cured with S/ODIP (1.5/1.93 phr) NR:MG30:NBR M100 (MPa) Tensile strength (MPa) 25:0: EB (%) *Oil swell ASTM#1 (%) :20.5: :0: :41: :0: :61.5: *Volume swelling after 70 h at 100 o C

45 SOLUBILITY PARAMETERS OF POLYMERS δ (Cal cm -3 ) ½ FKM 6 Q EPDM 7.9 PE/PP 8.0 PIB 8.0 Polyethylene PE 8.0 BR 8.1 NR 8.4 SBR 8.4 PS 8.7 Thiokol 9.2 CR 9.3 ACM 9.4 Amino Resins Epoxy Resins PVC 11.0 Nylons NBR 14.0